High resiliency, flexible polyurethane foams and crosslinkers for the preparation thereof

ABSTRACT

Reaction products of isocyanuric acid and derivatives thereof such as hydroxy-phenyl isocyanuric acid reacted with 1,2-epoxycontaining compounds such as a mixture of propylene oxide and phenyl glycidyl ether have been discovered to be effective substitutes for 4,4&#39;&#39;-methylene-bis(2-chloroaniline) as a crosslinker in high resiliency, flexible, polyurethane foams. The crosslinkers of the present invention are not presently suspected of being carcinogenic.

United States Patent 1 Gurgiolo 51 Sept. 23, 1975 1 1 HIGH RESILIENCY,FLEXIBLE POLYURETHANE FOAMS AND CROSSLINKERS FOR THE PREPARATION THEREOF(75] Inventor: Arthur E. Gurgiolo, Lake Jackson,

Tex.

[73] Assignee: The Dow Chemical Company,

Midland, Mich.

[22] Filed: Mar. 4, 1974 211 Appl. No.: 448,165

Related U.S. Application Data [63] Continuation-impart of Ser, No.410,138, Oct. 26.

[52] U.S. C1. ..260/2.5 AM; 260/25 AQ; 260/25 AW;260/77.5 AQ; 260/775 NC[51] Int. Cl. C08G 18/32; C08G 18/48; C08G 18/14 [58] Field ofSearch260/2.5 A0, 2.5 AM, 77.5 AQ,

260/25 AW, 77.5 NC

[56] References Cited UNITED STATES PATENTS 3,088,948 5/1963 Little260/307 C 3.730.923 5/1973 Formaini 260/25 AQ 3,738,953 6/1973 Anorga260/25 AM 3,756,970 9/1973 Bauchwitz.. 260/25 AC 3,766,181 10/1973Pregler 260/775 NC 3,772,221 11/1973 Hostettler... 260/25 AC 3,775,35011/1973 Junas 260/25 AM 3,795,636 3/1974 Huffman 260/25 AC 3,856,71812/1974 Taub v. 260/25 AQ Primary Examiner-M. 1. Welsh AssistantE.\aminerC. Warren lvy Attorney, Agent, or Firm.lames G. Carter [57]ABSTRACT 10 Claims, N0 Drawings HIGH RESILIENCY, FLEXIBLE POLYURETHANEFOAMS AND CROSSLINKERS FOR THE PREPARATION THEREOF This application is acontinuation-in-part of my previous application Ser. No. 410.138. filedOct. 26. 1973.

This invention relates to high resiliency. flexible poly urethane foamsand novel substances used as crosslinkers for the preparation thereof.

High resiliency, flexible polyurethane foams have heretofore beenprepared from polyether triols and polyisocyanates but the use of acrosslinker such as 4.4- '-methylene-bis(2-chloroaniline) has beenrequired. This compound has been suspected of being carcinogenic;therefore the urethane industry has been searching for suitablesubstitutes for this compound.

It has now been unexpectedly discovered that certain crosslinkersdescribed herein can suitably be substituted for the4,4-methylenebis(2-chloroaniline) in the preparation of flexible. highresiliency urethane foams and that these compounds are not at thepresent time suspected of being carcinogenic.

The present invention is therefore directed to flexible polyurethanefoams having a resiliency of greater than about 5071, a modulus of atleast about 2.3 resulting from subjecting to foaming conditions acomposition which comprises A. a polyol composition consistingessentially of 1. from about 50 to 100 and preferably from about 75 to100 parts by weight of a primary hydroxylcontaining polyether triolhaving an average bydroxyl equivalent weight of from about 900 to about2500.

2. from to about 50 and preferably from 0 to about 25 parts by weight ofa diol. a triol. a polymer-containing diol. a polymer-containing triolor mixtures thereof wherein said polyols have an average hydroxylequivalent weight of from about 900 to about 2500 and preferably fromabout 1000 to about 2000 and said polymer has an average molecularweight of at least about 5000 and preferably at least about. 20,000.

B. an organic polyisocyanate consisting of 1. from about 50 to 10071 andpreferably from about 75 to 100% by weight of 2.4toluene diisocyanate.2.6-toluene diisocyanate. NCO- containing prepolymers thereof. ormixtures thereof. and

2. from 0 to about 50% and preferably from about 0 to 2571 by weight ofan organic polyisocyanate having an average functionality of at least 2,

C. from about 1.0 to about 5 and preferably from about 2.0 to about 3.0parts by weight of water per 100 parts by weight of component (A).

D. from 0 to about and preferably from about 5 to about 10 parts of alow boiling auxiliary blowing agent per 100 parts by weight of component(A),

E. from about 1 to about 10 and preferably from about 3 to about 5 partsper 100 parts by weight of component (A) of a crosslinker compositionconsisting essentially of 1. from to 100 and preferably from 50 to 100percent by weight of a primary crosslinker component consisting of anoxyhydrocarbon or oxyhydrocarboxy derivative of isocyanuric acid or arylsubstituted isocyanuric acid or mixture thereof, and

2. from 0 to about and preferably from 0 to about 50 percent by weightof an auxiliary crosslinker component.

F. from about 0.5 to about 4 and preferably from about 0.7 to about 1.5parts by weight per parts by weight of Compound (A) of a catalyst forurethane formation;

(3. from about 0.005 to about 1.5 and preferably from about 0.03 toabout 0.05 parts by weight per 100 parts by weight of Component (A) of asilicone oil cell control agent; and wherein Components (A). (B). (C)and (E) are present in quantities so as to provide an NCOzactivehydrogen equivalent ratio of from about 08:10 to about 1.3:1.0 andpreferably from about 0.9:1.() to about l.l:l.0.

Suitable primary-hydroxyl containing triols which may be suitablyemployed as component (Al include the reaction products of glycerine.trimethylolpropane. hexane triol. mixtures thereof or the like. with a1.2 alkylene oxide having from 2 to about 4 carbon atoms or a mixture ofsuch alkylene oxides and subsequently endcapping the resultant polyolwith at least 1 mole of ethylene oxide per hydroxyl group and whereinthe resultant end-capped triol has an average hydroxyl equivalent weightof from about 900 to about 2500 and preferably from about 1200 to about2000. The primaryhydroxyl containing polyether polyol usually containsfrom about 4 to about 2071 by weight of ethylene oxide on the end of themolecule.

The term polymer-containing diols and triols which may be employed ascomponent (A-2) include those diols and triols having an averagehydroxyl equivalent weight in the range of from about 900 to about 2500and preferably from about 1000 to about 2000 and which contain fromabout 2 to about 50 and preferably from about 5 to about 20 parts byweight polymer having an average molecular weight of at least about5000, and preferably at least about 20,000.

Such polymers may be physically blended with the diol or triol or theymay be prepared in situ in the diol or triol wherein the diol or triol.or mixture thereof. are employed as the solvent or reaction medium forthe polymerization and in some instances. the polymers are grafted ontothe diol or triol.

Suitable such polymers and methods for their preparation are taught inU.S. Pat. Nos. 3.405.162; 3.652.639: 3.304.273; 3.383.351; and3.523.093. So much of those applications as pertains to polymers andmethods for their preparation are incorporated herein by reference.

The polymers may also be prepared by the aqueous emulsion techniquescommon to the latex" art or as a dispersion in a non-isocyanate reactivemedium. The polymers may be employed in the dry form. i.e. added to thetriol or diol after removal of the water or nonisocyanate reactivemedium therefrom or preferably the latex or dispersion itself may beadded to the diol or triol and the water or non-isocyanate reactivemedium subsequently removed therefrom by known procedures for removingwater or other components from polyols such as evaporation under vacuumand the like.

The polymers employed herein may contain groups which are reactive withthe NCO groups contained in the polyisocyanate. but it is not arequirement herein that said polymers contain such groups.

Particularly suitable polymers are those prepared by polymerizing one ormore monomers containing ethylenic unsaturation such as. for example.styrene. acrylic acid. mcthacrylic acid. acrylonitrile. butadiene.crotonic acid. itaconic acid. dimethylaminomethymethacrylate.acrylamidc. maleic acid. ethylacrylate. methylacrylate. butylacrylatc.methylmethacrylate. ethylmethacrylate. butylmethacrylate.Z-ethylhcxylacrylate. Z-ethylhexylmethacrylate. 'inyl monomethymaleate.

Suitable diols and triols which may be employed as component (A-Z)include those prepared by the reaction of a compound containing 2 or 3active hydrogen groups such as. for example. water. ethylene glycol.propylene glycol. 1.4-butane diol. l.6-hexane diol. glycerine.trimethylol propane. mixtures thereof and the like with a 1.2-epoxycompound such as ethylene oxide. 1.2-propylene oxide. 1.2-butylcneoxide. 2.3- butylene oxide. styrene oxide. mixtures thereof and the likeand which have an average hydroxyl equivalent weight of from about 900to about 2500 and preferably from about l()()() to about 2000. Alsosuitable are the polyester diols having an average hydroxyl equivalentweight of from about 900 to about 2500 and preferably from about 1000 toabout 2000.

Suitable organic polyisocyanates which may be employed in admixture withthe toluene diisocyanate or prepolymers thereofinclude any suchisocyanatc which does not contain a substituent group which is capableof reacting with the polyether triol. Suitable such isocyanates includepolymethylene polyphenylisoeyanate.

l .5naphthalenediisocyanate.

cumene-Z.4-diisocyanate.

4-methoxyl .3-phenylenediisocyanate.

4-chloro-l .3-phenylenediisocyanate.

4-bromo-l .3-phenylenediisocyanate.

4-ethoxy-l .3-phenylenediisocyanate.

isophoronediisocyanate.

2.4'-diisocyanatodiphenylether.

5.6-dimethyl-l .3-phenylenediisoeyanate.

2.4-dimethyll .3-phenylenediisocyanate.

4.4'-diisocyanatodiphenylether. benzidinediisocyanate.

4.6-dimethyl-l .3-phenylenediisocyanate.

4.4'-diisocyanatodibenzyl.

9.10-anthracenediisocyanate.3.3'-dimethyl-4.4'-diisocyanatodiphenylmethane.2.6-dimethyl-4.4-diisocyanatodiphenyl. 2.4-diisocyanatostilbene.3.3-dimethyl-4.4-diisocyanatodiphenyl.3.3-dimethoxy-4.4-diisoeyanatodiphenyl.

l .4-anthracencdiisocyanate.

2.5-fluorenediisocyanate.

l.8-naphthalenediisocyanate. 2.6-diisocyanatobenzfuran.2.4.6-toluenctriisocyanate. and 2.4.4-triisocyanatodiphenylether.

crude or undistilled isocyanates.

dimers or trimers of toluene diisocyanates.

Other organic polyisocyanates that can be used are the polyisocyanatesdescribed in Canadian Pat. No. 700.026 and in US. Pat. No. 2.683.730;the phenyl indane diisocyanates which are described in US. Pat. No.2.855.385. the organic diisocyanates and the organic triisocyanateswhich are described in US. Pat. No. 2.292.443; and the organictriisocyanates which are described in US. Pat. No. 2.929.794.

chloride. and

Suitable N('()-containing prepolymers of 2.4 and I.o-toluenediisocyanatewhich can be employed as the polyisocyanate component (Bl includes thoseprepared by reacting an excess of the toluenediisocyanate with asubstance having from 2 to abottt 4 active hydrogen atoms and an activehydrogen equivalent weight of from about 30 to about 2500. preferablyfrom about 30 to about 300.

Suitable such active hydrogen-containing substances include for example.ethylene diamine. ammonia. methyl amine. aminoethylethanol amine.propylene diamine. ethylene glycol. propylene glycol. butylene glycol.hexane diol. pentanediol. bisphenols. halogen substituted bisphcnols.neopcntyl glycol. halogenated neopentyl glycol. adducts of such activehydrogencontaining substances with vie-epoxy-containing compounds suchas for example. ethylene oxide. propylene oxide. 1.2-butylene oxide.2.3-butylene oxide. styrene oxide. epichlorohydrin. epibromohydrin.phenyl glycidyl ether. butyl glycidyl ether. dihromophenyl glycidylether. mixtures thereof and the like.

It is preferred that the NCO-containing prepolymer contain from about l0to about 45% free NCO groups by weight.

It should be understood that in the preparation of prepolymers from anexcess of the toluene diisocyanate. that the resultant product willusually contain some unreacted toluene diisocyanate.

Suitable oxyhydrocarbon or oxyhydrocarboxy derivatives of isocyanuricacid or aryl substituted isocyanurie acid which may be employed hereinare those represented by the general formula wherein R is =0 or a memberof the group represented by the formula RII wherein each R and R" areindependently hydrogen. Cl. Br. OH or an alkyl group having from 1 toabout 6 carbon atoms. each R,. R and R is independently selected fromthe formulas wherein each R. is independently hydrogen. phenyl. methyl.ethyl or halomethyl. each R and R.; are independently hydrogen or methylwith the proviso that only one of such groups can be a methyl group.each n is independently 0. l. 2 or 3; and

wherein R is selected from the group consisting of allyl, methallyl, anaryl group, a haloaryl group. a dihaloaryl group or an alkai'yl groupsaid aryl, haloaryl, dihaloaryl and alkaryl groups being represented bythe formula wherein Q is a halogen or an alkyl group and x has a valueof 1 when 0 is an alkyl group and a value of 1 or 2 when Q is a halogenor has a value ofzero', with the proviso that no more than 2 ofthe R Rand R groups can be represented by the formula when R is hydrogen,methyl or halomethyl.

Organotin catalysts such as stannous octoate, dibutyltindilaurate andthelike may also be employed together with the tertiary amine catalystif desired.

The above erosslinker compounds may be prepared by reacting theisocyanuric acid or an isocyanuric acid derivative with a 1,2-epoxidecontaining compound in a molar ratio of cyanuric acid toepoxide-containing compound of from about 1:2.5 to about 1:35 andpreferably from about l:2.9 to about 1:3.1 in the presence of a suitablebasic catalyst and a low polar or non-polar solvent or reaction mediumat temperatures of from about 80 to about 120 and preferably from aboutl()() to about 120C until the reaction is essentially complete andsubsequent removal of the solvent by conventional means.

In addition to isocyanuric acid, suitable isocyanuric acid derivativeswhich may be employed include, for example, Z-hydroxyphenyl isocyanuricacid, phenyl isocyanuric acid, methyl isocyanuric acid. ethylisocyanuric acid, butyl isocyanuric acid, propyl isocyanuric acid,mixtures thereof and the like.

Suitable l,2-epoxy-containing compounds which may be employed include,for example, ethylene oxide, l,2-propylcne oxide, 1,2-butylene oxide,2,3-butylene oxide, l,2-isobutylene oxide, epichlorohydrin, phenylglycidyl ether, butyl glycidyl ether, styrene oxide, mixtures thereofand the like.

Suitable basic catalysts which may be employed include sodium hydroxide,potassium hydroxide, benzyl trimethyl ammonium chloride, tetramethylammonium chloride, tetramethyl ammonium bromide, dodecyl dimethyl(2phenoxyethyl) ammonium bromide and the like,

Suitable solvents or reaction mediums which may be employed include, forexample, carbon tetrachloride, trichloromethane, dichloromethane, 1,2-dichloroethane, l,l,2,Z-tetrachloroethene, l,l,2,2- tetrachloroethane,1,1, l -trichloroethane, mixtures thereof and the like.

The isocyanuric acid from which many of the crosslinkers employed hereinare prepared is a well known article of commerce.

The aromatic and substituted aromatic isocyanuric acid derivatives fromwhich many of the crosslinkers are prepared may be prepared by thereaction of urea or hiuret with benzeldehyde, substituted benzaldehyde,benzal chloride or substituted benzal chloride as taught in.i--'IRIAZINI-.'S AN!) I)I-.'RIVA'I'IVI:'.S'. lnterscience Publishers,lnc., 195). pages Zl l-21.'1.

Suitable such compounds represented by the above formula which maybeemployed as a erosslinker herein include, for example,N-3-phenoxy-2-hydroxypropyl- N'-l\l" bis(2-hydroxypropyl)isoeyanurate.N-2-hydroxypropyl-N'-N" his(3-phenoxy-2-hydroxypropyl)isocyanurate.N-3-phenoxy-Z-hydroxypropyl- N'-N-bis(2-hydroxybutyl)isocyanurate.N-3-pmethylphenoxy-Z-hydrosypropyl-N'.Nbis(2-hydroxypropyl)isocyanurate, N-2-phenyl-Z-hydroxyethyl-N'- N -bis(Z-hydroxypropyl )isocyanurate. N,N',N tris( Z-hydroxypropyl)-phydroxyphenylisocyanurate, N,N,N "tris( Z-hydroxypropyl)-phenylisocyanurate, mixtures thereof and the like.

Suitable auxiliary erosslinker compounds include. for example,tris(polyoxyalkylene alkanol) amines; mono-, diand triisopropanolamines; oxydianiline; vicinal hydroxyl amines containing at least 4carbon atoms; mono-, di-, and triethanol amines; an aliphatic diol or apolyether diol, said diols having an OH equivalent weight of less thanabout 300 and preferably less than about 200;

Suitable tris(polyoxyalkylene alkanol) amines which may be employedherein include those represented by the formula N -+CH -CH-0+(H. (H 0+,,CH -(iHo|-l wherein each R is independently hydrogen, methyl or ethyl,and each n has an average value of from zero to about 5. The substancesrepresented by the above formula are readily prepared by thecondensation of ammonia with an alkylene oxide such as ethylene oxide,1,2-propylene oxide, 1,2-butylene oxide, l,2- isobutylenc oxide, ormixtures thereof. The products of the condensation reaction are mostgenerally a mixture of products, wherein the components of the mixturecan be, ifdesired, separated bydistillation or other suitable means orthe mixture itself can be employed as an auxiliary erosslinker.

Suitable vicinal hydroxyl amine compounds containing at least 4 carbonatoms which can be employed herein include, for example, thoserepresented by the general formulas:

wherein R R R and R are independently hydrogen, an alkyl group havingfrom 1 to about 10 carbon atoms, or a C-OR group wherein R is analiphatic hydrocarbon group having from I to about 10 carbon atoms, aphenyl group, a one to four carbon alkyl substituted phenyl group, or amono or dihalo substituted phenyl group, R is hydrogen, an aliphatichydrocarbon group having from 1 to about 10 carbon atoms, a by droxyalkyl group having from 1 to about 10 carbon atoms or a phenyl group andwherein n has a value of l to 3 inclusive, with the proviso that the sumof the carbon atoms contained in the R R R and R groups is at least 2.

" phenoxy-2-hydroxypropylamine,

wherein R and R collectively represent a divalent 3 to carbon atomsaturated'or unsaturated hydrocarbon group thereby forming a 5 to 8membered ring and wh" erein- R and n are as defined in formula labove.

cn oH I e i lreine ch R is independently hydrogen or an alkyl a grouphaving from l4 carbon atoms, each X is independently hydrogen, chlorine,bromine or-analkyl I group having from 14 carbon atoms and nhas a valueoffrom l to 3 inclusive.

Suitable vicina l hydroxyl amine compounds include, for example,l-amino-2-hydroxybutane, bis(2- hydroxybutyl) amine,tris(2-hydroxybutyl)amine, 3- 2phenyl-2- h-ydroxyethylamine,l-amino-2-hydroxycyclopentane, Z-hydroxypropyl-N-phenylamine,Z-hydroxyethyl-N- phenylamine, 3-phen0xy-2-hydroxypropyl-N- phenylamine,2-hydroxybutylrN-phenylamine, bis(3- phenoxy-2-hydroxypropyl) amine,Z-hydroxyethyl-N- (3-phenoxy-Z-hydroxypropyl )amine, l-amino-2-hydroxy-cyclohexane, l-amino-2-hydroxycyclooctane,2-hydroxyethyl-N-(2-hydroxybutyl)amine.

The vicinal hydroxyl amine compounds are readily prepared by reactingammonia, a primary or secondary amine or a primary or'secondary hydroxylamine with a vicinal epoxy-containing compound employing knownprocedures.

Suitable aliphatic diols which may be employed as a crosslinker hereininclude, for example, ethylene glycol, diethylene glycol. propyleneglycol. dipropylcne glycol, 1,2-butanc diol, l,3-butane diol, l,4-butane diol, mixtures thereof and the like.

Suitable polyether diols which may be employed as i a crosslinker hereininclude. for example, polyoxycthylene glycols, polyoxypropylenc glycols,polyoxybutylene glycols, mixtures thereof and the like.

Suitable silicone oils include polymers of dimethyl siloxane having aviscosity at 77C. of 5 centistokes or other silicone oils which arecommercially available.

Suitable auxiliary blowing agents include aliphatic hydrocarbons boilingbelow I 10C. or halogenated alilike. I 1

Organ'ometal catalysts such as stannous octoatcQ- dibutyltindilaurateand the'l ike may also'be employed either alone or together with thetertiary amine catalyst if desired. s

phatic hydrocarbons boiling below 1 10C. such as di- 60 Inorganic and;organic fillerssuch as. for example,

calcium'car'bonate. barytes. sand; expandable polystyrenc beads, and thelike may be includedin the foams of the present invention.

Fire retardant agents such as, for dibromopropyl)phosphate; phate;

tris( 2.-chloroethyl )phosp'loyed in the foamsof the" presentinvention".

. The crosslinker materials which arebelieved tobe new compositions ofmatter may be represented by the general formulas:

wherein R and R are independently selected from the group represented bythe formulas i wherein R is hydrogen or an alkyl group having from 1 toabout 3 carbon atoms; and

wherein R,, R and.R are independently selected from the grouprepresented by the general formulas example, tris(2,,3-

'tris(dichloropropyl) phosphate; I triethylphos I phate; mixturesthereof, and the-like may also be'emwherein R is hydrogen. an alkylgroup having 1 to 2 carbon atoms. aryl. alkaryl. haloaryl or haloalkyl.n has a value of l to about 4. R and R are independently hydrogen or amethyl group with the proviso that only one PREPARATION OF CROSSLINKERCOMPOUNDS --COMPONENT(E) i A series of crosslinker compounds wereprepared by.

ol such groups can be a methyl group. and R is sc-. 5 charging apressure container. eithera glass citrate bot-1 lected from the groupconsisting of allyl. methallyl. an tle or stainless steel bomb. with thereactants. catalyst aryl group. a haloaryl group. a dihaloaryl group.and an and solvent or reaction medium. The pressure conalkaryl group andwherein each R and R are mdepentainer was sealed and placed in anautoclave. After redently hydrogen. OH. or an alkyl group having frommoval from the autoclave. the solvent or reaction me. 1 to about 4carbon atoms. 10 dium and volatiles were removed by heating at reducedIt should be readily apparent from the description of pressure. Thereactants. solvent medium. catalyst reac-jz the preparation of thecrosslinkers employed herein tion conditions. and resultant products aregiven in the that they are mixtures of products which are reprefollowingTable I.

TABLE I Crosslinker Crosslinker ('rosslinkcr Crosslinker CrosslinkerCrosslinkcr C I) F. l-'

[socyanuric acid. grams/moles 97/075 65/05 645/05 645/05p-Hydroxyphenylisocyanuric acid. grams/moles 82/04 Phenylisocyanuricacid. g/molcs 9013/0474 [.2-Propylene oxide. grams/moles 2/2 [00/].72[00/1 .72 (O/l (i0/l Ethylene oxide. grams/moles Styrene oxide M Phenylglycidyl ether. grams/moles l l2/.75 w l.2-Butylene oxide. grams/moles[ms/[.07 (.resyl glycidyl ether. g/moles 82/05 Dibromophenyl glycidylether 4/05 Benzyl trimcthyl ammonium chloride. 60% aq. sol. grams 3 5 42 Z 2 CH Cl grams 70 [00 [00 Reaction Temperature. C [00 [[5 [00 [00 l[0 l [0 Reaction Time. hours 23 34 [38* [8 [8 l8 Product recovered.grams/V1 yield 293/99 [38.6/79 [20/70 [68/97 195/955 249/ 7: OH. byanalysis/theoretical l().7/l 2.9 ll.()'-)/l3.4 [Lo/[4.0 l4/l4.il [LS/HA8833/914 '71 N. by analysis/theorctical 10.4/[062 I [.34/1 [.02 9.7/[ [.5l [.4/[ 2.l5 [Lil/[0.27 743/7110 Visual description of product milky.reddish tan translucent milky tan translucent brown viscous colorless.viscous viscous syrup when tar tar viscous syrup tar hot which syrupsolidified to a glass when cooled Comparative Comparative CrosslinkerCrosslinker Crosslinker G H l lsocyanuric acid. grams/moles 20 lbs/0.15564.5/05 645/05 p-Hydroxyphenylisocyanuric acid. grams/molesPhenylisocyanuric acid. g/moles [,2-Propylcnc oxide. grams/moles 28.75lbs/ 0495 58/] Ethylene oxide. grants/moles 7().5/l.6 Styrene oxide60/05 Phenyl glycidyl ether. gms/moles [.2-Butylenc oxide. grams/molesCrcsyl glycidyl ether. g/moles Dibromophenyl glycidyl ether Bcnzyltrimethyl ammonium chloride. (10'71 aq. sol.. grams 44 2 5 CH CL grams31 lbs. [00*** 60 Reaction Temperature..C l [0 [0 Reaction Time. hours43 [5 Product recovered. grams/'7: yield [80/98 [35 7: OH. byanalysis/theoretical l3.4/[6.83 8.5/[40 [8.14/[ K N. byanalysis/thcoretical [0.5/1 [.5 5- l fi- Visual description of productViscous White tan tar Powder After 42 hours. some solid was stillpresent and l gram of triethylamine was added and the reaction wascontinued for an additional 96 hours. The propylene oxide was added at[20C to a [0 gallon pressure reactor containing the other componentsover a period of 24 hours after which the reaction mixture was digestedfor 24 hours at [20C. The product was recovered by filtering andflashing at 80C under vacuum.

PREPARATION OF HIGH RESILIENCY FOAMS In each of the following examples,all of the components except the isocyanate were blended together "untilthe components were equally dispersed. Then the isocyanate was quicklyadded and after stirring for several seconds the mixture was poured intoa vented closed mold and the mixture allowed to foam.

The compositions and the physical properties of the foams are given inthe following Table II.

TABLE ll ('ompara- Comparative 7 live FOAM l-OAM FOAM l-'()/\M FOAM FOAMFOAM FOAM FOAM No. A No. B No. No. D. No, l-'.. No. F No. (i No. H No. l

Polyol. 'l'ype/granis A/lllO A/l(l() A/llll) A/lUU A/Illt) A/lllll A/lllf) Allllt) A/lllU lolyisoeyanate. Type/grains A/3-l.4 A/3o.4 A/34.(\A/35 A/33.l [U335 .-\/34 AIS-Hi A1363 Water. grams 2.5 2.5 2.5 2.5 2.5.5 2.5 2.5 2.5 Silicone oil. grams .0} vU3 .03 .03 0.03 (MB 0.03 (1.03(1.03 Catalyst. Type/grunts A/lml /\/o.o A/(m A/(Hi A/(LS ,\/o.s ,\/o.s.-\/o.s A/(LX B/(Ll ll/(LZ li/(Ll l3/( .2 B/(Ll B/(Ll ll/lll ll/(LIll/(Ll (.rosslinker. Type/grams A/5 [3/5 (/5 l)/5 l-I/3 H5 (i/5 ll/S l/5Density. lhs/l't 2.88 3.0) 2.95 2.79 2.95 2.87 Foam 2.9. l-omn('ollapsed. Collapsed. Resiliency. l1 1 53 57 5l 49 5h o0 Properties 54Properties could could 25% ll.l) 37.7 45 38.6 33.5 37 7 not he 38 not bedetermined determined ILD 100 l l8 um )4 91.5 93.5 [(lll Modulus F 2.652 (1 2.75 .55 2.6] 2.66 2.63

Resiliency was determined by ASI M-l)-l 504-71.

"Modulus is the 65'; ll.l):'. i ll.l).

"ILD is Indentation Loud Deflection at 25'ri and 65"? by AS'I'MD-l5o-l-7l.

POLYOL A was the reaction product of glycerine with 20 propylene oxide,end capped with about 13-15% by weight of ethylene oxide and theresultant polyol had an OH equivalent weight of about 1650.

POLYISOCYANATE A was a crude toluene diisoeya- CATALYST A was a 33%solution of triethylene diamine in dipropylene glycol.

CATALYST B was bis( 2-dimethylaminoethyl)ether.

I claim: 1. A flexible polyurethane foam having a resiliency 1. from to100 percent by weight of a primary crosslinker component represented bythe general formula wherein each R,, R and R is independently selectedfrom the formulas greater than about 50%, a modulus of at least about2.3 35 and a density of less than about 5 lbs/ft resulting fromsubjecting to foaming conditions, a composition which comprises 1. fromabout to 100 parts by weight of a primary hydroxyl-containing polyethertriol containing an end-cap of at least 1 mole of ethylene oxide perhydroxyl group and having an average hydroxyl equivalent weight of fromabout 900 to about 2500;

2. from 0 to about 50 parts by weight of a polyol selected from a diol,a trio], or mixtures thereof wherein said diols and triols have anaverage hydroxyl equivalent weight of from about 900 to about 2500;

B. an organic polyisocyanate consisting of 1. from about 50 to 100% byweight of 2,4-toluene diisoeyanate; 2,6-toluene diisocyanate; NCO-containing prepolymers thereof or mixtures thereof and 2. from O toabout 50% by weight of an organic polyisocyanate having an average NCOfunctionality of at least 2;

C. from about 1.0 to about 5 parts by weight of water per 100 parts byweight of Component (A);

D. from about 0 to about 20 parts of a low boiling auxiliary blowingagent per 100 parts by weight of Component (A);

E. from about 1 to about 10 parts per I00 parts by weight of Component(A) of a crosslinker composition consisting essentially of wherein R andR are selected from the group consisting of hydrogen, methyl, ethyl,halomethyl, and phenyl with the proviso that when one of R and R isethyl, halomethyl, or phenyl the other is hydrogen; R is selected fromthe group consisting of allyl. mcthallyl or a group represented by theformula wherein Q is a halogen or an alkyl group and has a value of Iwhen Q is an alkyl group and a value of l or 2 when Q is a halogen or xhas a value of zero; wherein R, and R are selected from the groupconsisting of hydrogen, methyl. CH OR.;. and phenyl with the provisothat only one of R or R can be hydrogen and with the further provisothat when one of R or R is CH- ,OR or phenyl the other is hydrogen; andn has a value of l. 2 or 3; with the proviso that no more than 2 of theR,. R and R groups can he represented by the formula II when R or R ishydrogen methyl, or halomethyl when the other is hydrogen;

2. from to about 70 percent by weight of an auxiliary erosslinkercomponent;

F. from about 0.5 to about 4 parts by weight per 100 parts by weightofComponent (A) of a catalyst for urethane formation;

G. from about 0.005 to about l.5 parts by weight per 100 parts by weightof Component (A) ofa silicone oil cell control agent;

and wherein Components (A), (B), (C) and (E) are present in quantitiesso as to provide an NCOzactive hydrogen equivalent ratio of from about0.8210 to about 1.3: l .0.

2. The flexible polyurethane foam ofelaim I wherein Components (A). (B),(C) and (E) are employed in quantities so as to provide an NCOzactivehydrogen ratio of from about 0.9:l to about l.l:l. and Component (E) ispresent in quantities of from about 2 to about parts by weight per 100parts by weight of Component (A) and wherein Component (A) comprisesfrom 75-100 parts of (l) and 0-25 parts by 7. The foam of claim Iwherein Component (A-l) contains a polymer having a molecular weight ofat least about 5000.

8. The foam of claim 1 wherein in Component (E-l) 5 at least one of theR R R groups is the group ('H- -CH or (H. ,---CHCH --()R and the other RR and R groups are Z-hydroxylpropyl groups. 9. The foam of claim 8wherein R is the group 10. The foam of claim 8 wherein each of the R,. Rand R, groups are the group -CH CHCH CH

1. A FLEXIBLE POLYURETHANE FOAM HAVING A RESILIENCY GREATER THAN ABOUT50%, A MODULUS OF AT LEAST ABOUT 2.3 AND A DENSITY OF LESS THAN ABOUT5LBS/FT3 RESULTING FROM SUBJECTING TO FOAMING CONDITIONS, A COMPOSITIONWHICH COMPRISES A.
 1. FROM ABOUT 50 TO 100 PARTS BY WEIGHT OF A PRIMARYHYDROXYL-CONTAINING POLYETHER TRIOL CONTAINING AN ENDCAP OF AT LEAST 1MOLE OF ETHYLENE OXIDE PER HYDROXYL GROUP AND HAVING AN AVERAGE HYDROXYLEQUIVALENT WEIGHT OF FROM ABOUT 900 TO ABOUT 2500,
 1. FROM ABOUT 50 TO100% BY WEIGHT OF 2,4-TOLUENE DIISOCYANATE, 2,6-TOLUENE DIISOCYANATE,NCO-CONTAINING PREPOLYMERS THEREOF OR MIXTURES THEREOF AND
 1. FROM 30 TO100 PERCENT BY WEIGHT OF A PRIMARY CROSSLINKER COMPONENT REPRESENTED BYTHE GENERAL FORMULA
 2. FROM 0 TO ABOUT 50% BY WEIGHT OF AN ORGANICPOLYISOCYANATE HAVING AN AVERAGE NCO FUNCTIONALITY OF AT LEAST 2, C.FROM ABOUT 1.0 TO ABOUT 5 PARTS BY WEIGHT OF WATER PER 100 PARTS BYWEIGHT OF COMPONENT (A), D. FROM ABOUT 0 TO ABOUT 20 PARTS OF A LOWBOILING AUXILIARY BLOWING AGENT PER 100 PARTS BY WEIGHT OF COMPONENET(A), E. FROM ABOUT 1 TO ABOUT 10 PARTS PER 100 PARTS BY WEIGHT OFCOMPONENT (A) OF A CROSSLINKER COMPOSITION CONSISTING ESSENTIALLY OF 2.FROM 0 TO ABOUT 50 PARTS BY WEIGHT OF A POLYOL SELECTED FROM A DIOL, ATRIOL, OR MIXTURES THEREOF WHEREIN SAID DIOLS AND TRIOLS HAVE AN AVERAGEHYDROXYL EQUIVALENT WEIGHT OF FROM ABOUT 900 TO ABOUT 2500, B. ANORGANIC POLYISOCYANATE CONSISTING OF
 2. The flexible polyurethane foamof claim 1 wherein Components (A), (B), (C) and (E) are employed inquantities so as to provide an NCO:active hydrogen ratio of from about0.9:1 to about 1.1:1, and Component (E) is present in quantities of fromabout 2 to about 5 parts by weight per 100 parts by weight of Component(A) and wherein Component (A) comprises from 75-100 parts of (1) and0-25 parts by weight of (2).
 2. from 0 to about 70 percent by weight ofan auxiliary crosslinker component; F. from about 0.5 to about 4 partsby weight per 100 parts by weight of Component (A) of a catalyst forurethane formation; G. from about 0.005 to about 1.5 parts by weight per100 parts by weight of Component (A) of a silicone oil cell controlagent; and wherein Components (A), (B), (C) and (E) are present inquantities so as to provide an NCO:active hydrogen equivalent ratio offrom about 0.8:1.0 to about 1.3:1.0.
 2. from 0 to about 50% by weight ofan organic pOlyisocyanate having an average NCO functionality of atleast 2; C. from about 1.0 to about 5 parts by weight of water per 100parts by weight of Component (A); D. from about 0 to about 20 parts of alow boiling auxiliary blowing agent per 100 parts by weight of Component(A); E. from about 1 to about 10 parts per 100 parts by weight ofComponent (A) of a crosslinker composition consisting essentially of 2.from 0 to about 50 parts by weight of a polyol selected from a diol, atriol, or mixtures thereof wherein said diols and triols have an averagehydroxyl equivalent weight of from about 900 to about 2500; B. anorganic polyisocyanate consisting of
 2. FROM 0 TO ABOUT 70 PERCENT BYWEIGHT OF AN AUXILIARY CROSSLINKER COMPONENT, F. FROM ABOUT 0.5 TO ABOUT4 PARTS BY WEIGHT PER 100 PARTS BY WEIGHT OF COMPONENT (A) OF A CATALYSTFOR URETHANE FORMATION, G. FROM ABOUT 0.005 TO ABOUT 1.5 PARTS BY WEIGHTPER 100 PARTS BY WEIGHT OF COMPONENT (A) OF A SILICONE OIL CELL CONTROLAGENT, AND WHEREIN COMPONENTS (A), (B), (C) AND (E) ARE PRESENT INQUANTITIES SO AS TO PROVIDE AN NCO:ACTIVE HYDROGEN EQUIVALENT RATIO OFFROM ABOUT 0.8:1.0 TO ABOUT 1.3:1.0.
 3. The flexible polyurethane foamof claim 2 wherein Component (E1) is present in quantities of from about50 to about 100 percent and Component (E2) is present in from about 0 toabout 50 percent.
 4. The flexible polyurethane foam of claim 3 whereinComponent E consists of 100 percent of Component (E1).
 5. The flexiblepolyurethane foam of claim 4 wherein Component (A-1) is a glycerineinitiated polyether polyol.
 6. The flexible polyurethane foam of claim 5wherein Component (A2) is absent from the composition.
 7. The foam ofclaim 1 wherein Component (A-1) contains a polymer having a molecularweight of at least about
 5000. 8. The foam of claim 1 wherein inComponent (E-1) at least one of the R1, R2, R3 groups is the group 9.The foam of claim 8 wherein R6 is the group
 10. The foam of claim 8wherein each of the R1, R2 and R3 groups are the group -CH2-CH-CH2-CH3.